CN1290926C - Lactic acid polymer composition and molded object thereof - Google Patents

Abstract

Disclosed herein are a lactic acid-based polymer composition comprising: (i) an amide compound represented by General Formula (1): wherein R1 represents a C2-30 saturated or unsaturated aliphatic polycarboxylic acid residue, a C4-28 saturated or unsaturated alicyclic polycarboxylic acid residue, or a C6-28 aromatic polycarboxylic acid residue, and R2 represents C1-18 alkyl, C2-18 alkenyl, C3-12 cycloalkyl or cycloalkenyl or the like, (ii) an ester plasticizer, and (iii) a lactic acid-based polymer; a transparent, crystalline (heat resistant) molded article molded from such a lactic acid-based polymer composition; and a method for producing such a molded article.

Description

Lactic acid polymer composition and molded article thereof

technical field

The present invention relates to a lactic acid-based polymer composition containing a lactic acid-based polymer composition, and a molded article of the lactic acid-based polymer composition formed from the lactic acid-based polymer composition.

Background technique

In recent years, from the viewpoint of nature conservation, disposal of commonly used plastics such as polyethylene, polypropylene, polystyrene, and polyvinyl chloride, which do not decompose in natural environments, after use has become a problem. Most of these commonly used plastics are not reused or recycled, and are disposed of through burning and landfilling. However, when burning commonly used plastics, polyethylene, polypropylene, and polystyrene have high burning calories, which are easy to damage the burner. In addition, it is known that polyvinyl chloride generates harmful gases such as dioxin. When burying these commonly used plastics, these commonly used plastics are chemically stable and tend to remain semi-permanently, causing a profound reason for the lack of land for burial.

In order to solve these problems, biodegradable polymers and molded products that can be decomposed in the natural environment are required. For copolymers of 3-hydroxybutyric acid and 3-hydroxyvaleric acid, polycaprolactone, and polybutylene succinate Research on naturally decomposable resins such as aliphatic carboxylic acid polyesters is ongoing. One of them is polylactic acid and its copolymers. Lactic acid-based polymers are characterized by biodegradability, and the calories burned are about 1/3 to 1/2 lower than polyethylene and polypropylene. There is no harm to the furnace. In addition, NOx and SOx are not produced during combustion In particular, no toxic gas such as dioxin is generated. Furthermore, lactic acid-based polymers use annual renewable plant resources (corn starch, etc.) as starting materials, so fossil resources such as petroleum can not be used, and they can be expected to replace common plastics.

On the other hand, in recent years, with the rapid development of technology development in the fields of electronics, machinery, optoelectronic engineering, laser, liquid crystal, optics, office automation, factory automation, etc., the demand for transparent films has increased rapidly, and its applications have also leapt. expanding. Specific examples include films for overhead projectors, films for plate making, films for write-through, films for food packaging, films for agriculture, transparent conductive films (for example, touch screens for computer input screens), heat reflection films, Films for liquid crystal displays, polarizing films for liquid crystal displays, printed circuit boards, etc.

In the past, in these applications, glass, acrylate (polymethyl methacrylate), polycarbonate, and other low-flexibility hard films were used, but recently, flexibility, ease of molding, and heat resistance are used. The trend of replacing them with transparent films with excellent performance is rapidly proceeding. A polyethylene terephthalate (PET) film can be used as a part of such an alternative film, but PET still has problems in terms of applications requiring biodegradation or decomposition in natural environments. Against such a background, in the technical field of transparent films, the roles played by transparent films having transparency, heat resistance (crystallinity), and decomposability are expected to be significant.

However, polylactic acid which is a decomposable thermoplastic polymer, a copolymer of lactic acid and other compounds having two or more ester bond-forming functional groups (for example, aliphatic hydroxycarboxylic acid, lactone, etc.) Lactic acid-based polymer molded articles are usually non-crystalline after molding, and crystals as large as the wavelength of light constituting the cause of scattered light hardly exist, so they are transparent. However, molded articles obtained from these lactic acid polymers are generally non-crystalline, and therefore have poor heat resistance. Therefore, for example, an amorphous polylactic acid container has excellent transparency, but has low heat resistance, cannot be in contact with hot water, and cannot be used for heating in a microwave oven, so its use is limited.

For this reason, in order to improve the heat resistance of the lactic acid polymer molded article, during the molding process, it is filled into a metal mold kept near the crystallization temperature for a long time, or the non-crystalline molded article is subjected to heat treatment after molding ( annealing) and other heat treatments, however, as crystallization progresses, crystals (such as spherulites) that are larger than the wavelength of the light that constitutes the cause of scattered light usually grow rapidly to a size larger than that of visible light, and the molded body becomes opaque.

In the technical field related to lactic acid polymers, for example, by adding the following additives and nucleating agents to inhibit the growth of spherulites, impart transparency or accelerate the crystallization rate, and improve the crystallinity technology has been disclosed, but from the process From the point of view, its effect may not be sufficient.

1) The technology to obtain an aliphatic polyester molded product with both transparency and crystallinity by blending 0.1 to 10 parts by weight of an aliphatic carboxylic acid amide with a melting point of 40 to 300°C in polylactic acid-based aliphatic polyester public. This technique is characterized in that crystallinity is improved by heat treatment during or after molding under general molding conditions, but only examples in which heat treatment is performed after molding are described. In this method, since it enters a new heat treatment process after molding, and the molded product is greatly deformed with the progress of crystallization during heat treatment, it may not be said to be an industrially advantageous method (see JP-A-9-278991 Bulletin).

2) It has been disclosed that by adding an amide compound having a specific structure to polylactic acid resin, the crystallinity of polylactic acid resin is improved, and the release property of the metal mold is improved. However, in the examples, there is no description of an example in which mold release properties are improved, and there is no description of the characteristics of both transparency and crystallinity (see JP-A-10-87975).

Judging from the technologies described in these literatures, it cannot but be said that it is industrially quite difficult to simultaneously impart transparency and crystallinity to lactic acid-based molded articles in the current situation.

disclosure of invention

An object of the present invention is to provide a lactic acid-based polymer composition capable of producing a molded article having both transparency and crystallinity (heat resistance), and a molded article obtained by molding the lactic acid-based polymer composition.

As a result of diligent research by the present inventors in order to achieve the above object, the following findings have been obtained.

① When adding a specific amide compound and ester plasticizer to a lactic acid polymer, and molding the obtained lactic acid polymer composition (or after molding), through the crystallization process of the lactic acid polymer, due to the The synergistic effect of the compound and the ester-based plasticizer yields a molded product with transparency and crystallinity (heat resistance).

②In the above crystallization process, the molding cycle can be shortened by increasing the crystallization rate.

Based on such knowledge, the present invention has been completed through repeated studies, and provides the following molded article of a lactic acid-based polymer composition.

Item 1. A lactic acid polymer composition characterized by containing at least (i) at least one amide compound represented by general formula (1), (ii) at least one ester plasticizer, and (iii) Lactic acid-based polymers.

[wherein, R ¹ represents a saturated or unsaturated aliphatic polycarboxylic acid residue with 2 to 30 carbon atoms, especially 4 to 10, and a saturated or unsaturated aliphatic polycarboxylic acid residue with 4 to 28 carbon atoms, especially 5 to 10 Alicyclic acid polycarboxylic acid residues, or aromatic polycarboxylic acid residues having 6 to 28 carbon atoms, especially 6 to 12 carbon atoms.

^R2 represents an alkyl group with 1 to 18 carbon atoms, especially 4 to 10 carbon atoms, an alkenyl alkenyl group with 2 to 18 carbon atoms, especially 4 to 10 carbon atoms, or an alkenyl alkenyl group with 3 to 12 carbon atoms, especially 5 to 8 carbon atoms. Cycloalkyl or cycloalkenyl, phenyl, naphthyl, anthracenyl, or groups represented by general formula (a), general formula (b), general formula (c), general formula (d);

In each of the above formulas, R ^{represents an} alkyl group with 1 to 18 carbon atoms, especially 1 to 4 carbon atoms, an alkenyl group with 2 to 18 carbon atoms, especially 4 to 10 carbon atoms, an alkenyl group with 1 to 18 carbon atoms, especially An alkoxy group with 1 to 4 carbon atoms, a cycloalkyl group with 3 to 18 carbon atoms, especially a cycloalkyl group with 5 to 12 carbon atoms, a phenyl group or a halogen atom; ^R4 represents a straight chain or branched chain alkylene group with 1 to 4 carbon atoms , R ⁵ and R ⁶ have the same definition as R ³ above, R ⁷ has the same definition as R ⁴ above, and R ⁸ has the same definition as R ³ above.

a is an integer of 2 to 6, especially 2 to 4, b is an integer of 1 to 5, especially 1 to 3, c is an integer of 0 to 5, especially 0 to 3, and d is an integer of 1 to 5, especially An integer of 1-3, e is an integer of 0-5, especially 0-3. ]

Item 2. The lactic acid-based polymer composition according to item 1 above, wherein ^R represents 1,4-cyclohexanedicarboxylic acid residue, 2,6-naphthalene dicarboxylic acid residue, trimene acid residues or 1,2,3,4-butanetetracarboxylic acid residues.

Item 3. The lactic acid-based polymer composition according to the above item 1, wherein R ¹ represents a trimesic acid residue.

Item 4. The lactic acid-based polymer composition according to Item 1 above, wherein ^R represents 1,4-cyclohexanedicarboxylic acid residue, 2,6-naphthalene dicarboxylic acid residue, trimene Acid residue or 1,2,3,4-butane tetracarboxylic acid residue, R ² represents tert-butyl, cyclohexyl, phenyl, 2-methylcyclohexyl, 4-methylcyclohexyl or benzyl.

Item 5. The lactic acid-based polymer composition according to item 4 above, wherein the amide-based amine compound is composed of at least one selected from the following compounds, namely trimesic acid tricyclohexylamide, benzene Tris(2-methylcyclohexylamide) trimesate, Tris(4-methylcyclohexylamide) trimesate, 1,4-cyclohexanedicarboxylic acid dicyclohexylamide, 1,4-cyclohexyl Alkanedicarboxylic acid bis(2-methylcyclohexylamide), 1,4-cyclohexanedicarboxylic acid dibenzylamide, 2,6-naphthalene dicarboxylic acid dicyclohexylamide, 1,2,3,4 - Butanetetracarboxylic acid tetracyclohexylamide and 1,2,3,4-butanetetracarboxylic acid tetraanilide.

Item 6. The lactic acid-based polymer composition according to any one of items 1 to 5 above, wherein the ester-based plasticizer is selected from polyol derivatives, hydroxycarboxylic acid derivatives, aliphatic or aromatic carboxyl At least one selected from the group consisting of esters, polyether polyol derivatives, and phosphoric acid derivatives.

Item 7. The lactic acid-based polymer composition according to item 6 above, wherein the ester-based plasticizer is selected from the group consisting of glycerol derivatives, citric acid derivatives, and polyalkylene glycols. at least one of .

Item 8. The lactic acid-based polymer composition according to item 7 above, wherein the glycerin derivative is glycerol trialiphatic carboxylic acid ester (aliphatic carboxylic acid: 2 to 18 carbon atoms) at least one.

Item 9. The lactic acid-based polymer composition according to item 7 above, wherein the citric acid derivative is obtained from acetyl trialkyl citrate (alkyl: 1 to 18 carbon atoms) and trialkyl citrate At least one selected from the group consisting of alkyl esters (alkyl: 1 to 18 carbon atoms).

Item 10. The lactic acid-based polymer composition according to item 7 above, wherein the polyalkylene glycol derivative is at least one selected from the following compounds, namely, diethylene glycol dialiphatic carboxylic acid Esters (aliphatic carboxylic acid: 2 to 18 carbon atoms), triethylene glycol dialiphatic carboxylic acid ester (aliphatic carboxylic acid: 2 to 18 carbon atoms), tetraethylene glycol dialiphatic carboxylic acid ester (aliphatic Carboxylic acid: 2 to 18 carbon atoms), polyethylene glycol dialiphatic carboxylate (aliphatic carboxylic acid: 2 to 18 carbon atoms), diethylene glycol diaromatic carboxylate, triethylene glycol diaromatic carboxylate Aromatic carboxylate, tetraethylene glycol diaromatic carboxylate, polyethylene glycol diaromatic carboxylate, dipropylene glycol dialiphatic carboxylate (aliphatic carboxylic acid: carbon number 2 to 18), tripropylene glycol Dialiphatic carboxylate (aliphatic carboxylic acid: 2 to 18 carbon atoms), tetrapropylene glycol dialiphatic carboxylate (aliphatic carboxylic acid: 2 to 18 carbon atoms), polypropylene glycol dialiphatic carboxylate (aliphatic carboxylic acid: 2 to 18 carbon atoms), dipropylene glycol diaromatic carboxylate, tripropylene glycol diaromatic carboxylate, tetrapropylene glycol diaromatic carboxylate, and polypropylene glycol diaromatic carboxylate .

Item 11. The lactic acid-based polymer composition according to any one of items 1 to 10 above, wherein the above-mentioned lactic acid-based polymer has a weight average molecular weight of 50,000 or more.

Item 12. The lactic acid polymer composition according to any one of items 1 to 11 above, wherein 0.01 to 10 parts by weight of an amide compound and an ester plasticizer are contained with respect to 100 parts by weight of the lactic acid polymer. 1 to 300 parts by weight.

Item 13. A molded article obtained by molding the lactic acid-based polymer composition according to any one of Items 1 to 12.

Item 14. A transparent molded article composed of the lactic acid-based polymer composition described in any one of the above items 1 to 12, having a crystallinity of 30% or more, and having a thickness of 0.5 mm, which is foggy Degree is 70% or less.

The fifteenth invention is a production method, which is the production method of the lactic acid-based polymer molded body described in the above-mentioned fourteenth item, which comprises the following steps:

1) filling the melt of the lactic acid polymer composition in granular form into a metal mold to crystallize it in the metal mold, or

2) Extrude the melt of the lactic acid-based polymer composition in granular form from a T-die extrusion molding machine, crystallize it with a chilled roll,

The crystallization is carried out at a temperature between Tc and Tg (wherein, Tc is the temperature at which the crystallization of the lactic acid-based polymer composition starts, which is obtained by measuring the composition of the lactic acid-based polymer by differential scanning calorimetry, and Tg is The glass transition temperature of the lactic acid-based polymer composition).

Hereinafter, the present invention will be described in detail.

Amide compounds

The amide compound represented by the general formula (1) in the present invention is obtained by converting an aliphatic, alicyclic or aromatic compound represented by the general formula (1a) to carboxylic acids, their anhydrides, alkyl esters (especially C ₁ -C ₄ alkyl esters) or chlorides and one or more aliphatic, alicyclic or aromatic compounds represented by general formula (2) It is easily obtained by amidation of monoamine compounds.

[wherein, R ⁹ has the same definition as the above-mentioned R ¹ , and f has the same definition as the above-mentioned a]

R ¹⁰ -NH ₂ (1b)

[wherein, R ¹⁰ has the same definition as R ² above]

Therefore, the "polycarboxylic acid residue" represented by R in the general formula ( ¹ ) is represented by the above-mentioned general formula (1a) except all the aliphatic, alicyclic or aromatic carboxylic acids exemplified below. The residue obtained from the carboxyl group. In addition, the number of carbon atoms described in R ¹ refers to the number of carbon atoms contained in the "polycarboxylic acid residue" (R ⁹ =R ¹ ) obtained by removing the carboxyl group. In addition, R ² of the general formula (1) is a residue obtained by removing all carboxyl groups from an aliphatic, alicyclic or aromatic carboxylic acid exemplified below, represented by the above general formula (1b).

As the aliphatic polycarboxylic acid can be mentioned in the general formula (1a) R ⁹ is an aliphatic carboxyl with 2 to 30 carbon atoms, especially 4 to 10, and 2 to 6 (especially 2 to 4) carboxyl groups. acid. For example, biphenylmalonic acid, succinic acid, phenylsuccinic acid, biphenylsuccinic acid, glutaric acid, 3,3-dimethylglutaric acid, adipic acid, pimelic acid, octane Diacid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,18-octadecanedioic acid, citric acid, methanetricarboxylic acid acid, propane tricarboxylic acid, propene tricarboxylic acid, pentane tricarboxylic acid, ethane tetracarboxylic acid, propane tetracarboxylic acid, pentane tetracarboxylic acid, butane tetracarboxylic acid (especially 1,2,3,4 -butane tetracarboxylic acid), dodecane tetracarboxylic acid, pentane pentacarboxylic acid, tetradecane hexacarboxylic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, ethylene glycol bis(β-aminoethyl ether) N, N, N', N'-tetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethylethylenediamine-N, N', N'-triacetic acid, 1,3-diamino Propan-2-ol-N,N,N',N'-tetraacetic acid, 1,2-diaminopropan-2-ol-N,N,N',N'-tetraacetic acid triethylenetetraminehexaacetic acid , Nitrilotripropionic acid, 1,6-hexanediaminetetraacetic acid, N-(2-carboxyethyl)iminodiacetic acid, etc.

As the alicyclic polycarboxylic acid, in the general formula (1a), ^R9 is a fat having 4 to 28 carbon atoms, especially 5 to 10, and 2 to 6 (especially 2 to 4) carboxyl groups. Cyclic carboxylic acid. For example, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid, 1,5-decalanedicarboxylic acid, 2,6 -Decalin dicarboxylic acid, 4,4'-dicyclohexane dicarboxylic acid, cyclohexane tricarboxylic acid, cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, tetrahydrofuran tetracarboxylic acid Carboxylic acid, 5-(butanedioic acid)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6 - Tetracarboxylic acid, cyclohexanehexacarboxylic acid, 5,6,9,10-tetracarboxytricyclo[6.2.2.0 ^2.7 ]dodecyl-2,11-diene and its lower alkyl substituents (e.g. , 3, 8, 11 or 12 methyl substitutions), 1,2-cyclohexanediaminetetraacetic acid, 2,3,5-tricarboxycyclopentyl carboxylic acid, 6-methyl- 4-cyclohexene-1,2,3-tricarboxylic acid, 3,5,6-tricarboxynorbornane-2-acetic acid, thiobis(norbornane-2,3-dicarboxylic acid), bicyclo [4.2.0] Octane-3,4,7,8-tetracarboxylic acid, 1,1'-dicyclopropane-2,2',3,3'-tetracarboxylic acid, 1,2-bis(2 , 3-Dimethyl-2,3-dicarboxycyclobutyl)ethane, pyrazine-2,3,5,6-tetracarboxylic acid, tricyclo[4.2.2.0 ^2.5 ]decyl-9-ene -3,4,7,8-tetracarboxylic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene dioic acid and its lower alkyl substituents (for example, 1-position, 5, 6 or 7 methyl substitutions), 2,3,4,5,6,7,12,13-octahydrophenanthrene-3,4,5,6-tetracarboxylic acid, etc.

As the aromatic polycarboxylic acid, it can be mentioned that in general formula (1a), ^R9 is an aromatic group having 6 to 28 carbon atoms, especially 6 to 12, and 2 to 6 (especially 2 to 4) carboxyl groups. carboxylic acid. For example, specifically, terephthalic acid, terephthalic acid, phthalic acid, 4-tert-butylphthalic acid, isophthalic acid, 5-tert-butylisophthalic acid, terephthalic acid , 1,8-naphthoic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, biphenyl acid, 3,3'-biphenyl dicarboxylic acid , 4,4'-biphenyl dicarboxylic acid, 4,4'-binaphthyl dicarboxylic acid, bis(3-carboxyphenyl)methane, bis(4-carboxyphenyl)methane, 2,2-bis (3-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)propane, 3,3'-sulfonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 3,3'- Hydroxydibenzoic acid, 4,4'-hydroxydibenzoic acid, 3,3'-oxodibenzoic acid, 4,4'-oxodibenzoic acid, 3,3'-thiodibenzoic acid, 4,4'- Thiodibenzoic acid, 4,4'-(p-phenylenedioxy)dibenzoic acid, 4,4'-isophthaloyldibenzoic acid, 4,4'-terephthaloyldiphenyl Formic acid, dithiosalicylic acid, benzene tricarboxylic acid, benzene tetracarboxylic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, biphenyl sulfone tetracarboxylic acid (especially Yes, 3,3',4,4'-biphenylsulfone tetracarboxylic acid), biphenylmethane tetracarboxylic acid, perylene tetracarboxylic acid, naphthalene tetracarboxylic acid, 4,4'-binaphthalene dicarboxylic acid, biphenyl Aniline-3,3'-dicarboxy-N,N'-tetracarboxylic acid, biphenylpropane tetracarboxylic acid, anthracene tetracarboxylic acid, phthalocyanine tetracarboxylic acid, ethylene glycol-trimellitic acid diester, Mellitic acid, glycerol-trimellitic acid triester, etc.

Examples of aliphatic monoamines include saturated aliphatic monoamines having 1 to 18 carbon atoms, especially 4 to 10 carbon atoms, and aliphatic monoamines having one carbon-carbon double bond having 2 to 18 carbon atoms, especially 4 to 10 carbon atoms. monoamine. For example, specifically, methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, tert-amylamine, hexylamine, heptylamine, n-octylamine , 2-ethylhexylamine, tert-octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine Alkylamine, heptadecylamine, octadecylamine, allylamine, etc.

Examples of the alicyclic monoamine include alicyclic monoamines having 3 to 12 carbon atoms, particularly 5 to 8 carbon atoms. For example, specifically, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, cyclododecylamine, etc., and the general formula ( 2) or the compound represented by (3).

[wherein, R ¹¹ represents an alkyl group with 1 to 18 carbon atoms, an alkenyl group with 2 to 18 carbon atoms, an alkoxy group with 1 to 18 carbon atoms, a cycloalkyl group with 3 to 18 carbon atoms, phenyl or halogen atom. g is an integer of 1-5. ]

[In the formula, ^R12 represents a linear or branched alkylene group having 1 to 4 carbon atoms. R ¹³ represents the same definition as R ¹¹ above. h is an integer of 0-5. ]

Specific examples of the alicyclic monoamine represented by the general formula (2) include methylcyclohexylamine, ethylcyclohexylamine, propylcyclohexylamine, isopropylcyclohexylamine, t-butylcyclohexylamine, n-Butylcyclohexylamine, isobutylcyclohexylamine, sec-butylcyclohexylamine, n-pentylcyclohexylamine, isopentylcyclohexylamine, sec-pentylcyclohexylamine, tert-amylcyclohexylamine, hexylcyclohexylamine, heptyl Cyclohexylamine, Octylcyclohexylamine, Nonylcyclohexylamine, Decylcyclohexylamine, Undecylcyclohexylamine, Dodecylcyclohexylamine, Cyclohexylcyclohexylamine, Phenylcyclohexylamine, Dimethylcyclohexylamine, diethylcyclohexylamine, dipropylcyclohexylamine, diisopropylcyclohexylamine, di-n-butylcyclohexylamine, di-sec-butylcyclohexylamine, di-tert-butylcyclohexylamine, di-n-pentylamine Cyclohexylamine, di-tert-pentylcyclohexylamine, dihexylcyclohexylamine, trimethylcyclohexylamine, triethylcyclohexylamine, tripropylcyclohexylamine, triisopropylcyclohexylamine, tri-n- Butylcyclohexylamine, tri-sec-butylcyclohexylamine, tri-tert-butylcyclohexylamine, methoxycyclohexylamine, ethoxycyclohexylamine, dimethoxycyclohexylamine, diethoxycyclohexylamine, di-n-butoxy Cyclohexylamine, di-sec-butoxycyclohexylamine, di-tert-butoxycyclohexylamine, trimethoxycyclohexylamine, tri-n-butoxycyclohexylamine, chlorocyclohexylamine, dichlorocyclohexylamine, Methylchlorocyclohexylamine, trichlorocyclohexylamine, bromocyclohexylamine, dibromocyclohexylamine, tribromocyclohexylamine, etc.

Specific examples of the alicyclic monoamine represented by the general formula (3) include cyclohexylmethylamine, methylcyclohexylmethylamine, dimethylcyclohexylmethylamine, trimethylcyclohexylmethylamine, methoxy Cyclohexylmethylamine, ethoxycyclohexylmethylamine, dimethoxycyclohexylmethylamine, chlorocyclohexylmethylamine, dichlorocyclohexylmethylamine, α-cyclohexylethylamine, β-cyclohexylethylamine, Methoxychlorocyclohexylethylamine, dimethoxychlorocyclohexylethylamine, chlorocyclohexylethylamine, dichlorocyclohexylethylamine, α-cyclohexylpropylamine, β-cyclohexylpropylamine, γ-cyclohexylpropylamine, Methylcyclohexylpropylamine, etc.

Examples of the aromatic monoamine include aniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene, and compounds represented by the general formula (4) or (5).

[wherein, R ¹⁴ represents the same definition as above R ¹¹ . i is an integer of 1-5. ]

[In the formula, R ¹⁵ represents the same definition as R ¹² above, and R ¹⁶ represents the same definition as R ¹¹ above. j is an integer of 0-5. ]

The aromatic monoamine represented by the general formula (4) specifically includes toluidine, ethylaniline, propylaniline, p-cumylamine, tert-butylaniline, n-butylaniline, isobutylaniline, Aniline, sec-butylaniline, n-pentylaniline, isopentylaniline, sec-amylaniline, tert-amylaniline, hexylaniline, heptylaniline, octylaniline, nonylaniline, decylaniline, undecylaniline Aniline, dodecylaniline, cyclohexylaniline, aminodiphenyl, aminostyrene, dimethylaniline, diethylaniline, dipropylaniline, diisopropylaniline, di-n-butylaniline, di-sec Butylaniline, di-tert-butylaniline, trimethylaniline, triethylaniline, tripropylaniline, tri-tert-butylaniline, o-methoxyaniline, ethoxyaniline, dimethoxyaniline, diethylaniline oxyaniline, trimethoxyaniline, tri-n-butoxyaniline, chloroaniline, dichloroaniline, trichloroaniline, bromoaniline, dibromoaniline, tribromoaniline, etc.

The aromatic monoamine represented by the general formula (5) specifically includes benzylamine, methylbenzylamine, dimethylbenzylamine, trimethylbenzylamine, methoxybenzylamine, ethyl Oxybenzylamine, dimethoxybenzylamine, chlorobenzylamine, dichlorobenzylamine, α-phenylethylamine, β-phenylethylamine, methoxyphenylethylamine, dimethoxybenzylamine phenylethylamine, chlorophenylethylamine, dichlorophenylethylamine, α-phenylpropylamine, β-phenylpropylamine, γ-phenylpropylamine, methylphenylpropylamine, etc.

Among the above-mentioned amide compounds, particularly ^R in the general formula (1) is 1,4-cyclohexanedicarboxylic acid residue, 2,6-naphthalene dicarboxylic acid residue, trimesic acid residue or 1 , 2,3,4-butanetetracarboxylic acid residues are preferred, and particularly preferred are compounds in which ^R is a trimesic acid residue.

Among these, ^R in the general formula (1) is 1,4-cyclohexanedicarboxylic acid residue, 2,6-naphthalene dicarboxylic acid residue, trimesic acid residue or 1,2,3 , 4-butane tetracarboxylic acid residue, R ² is a compound of tert-butyl, cyclohexyl, phenyl, 2-methylcyclohexyl, 4-methylcyclohexyl or benzyl is preferred.

Among the amide compounds represented by general formula (1) in the present invention, particularly recommended are trimesic acid tricyclohexylamide, trimesic acid tris(2-methylcyclohexylamide), trimesic acid Tris(4-methylcyclohexylamide), 1,4-cyclohexanedicarboxylic acid dicyclohexylamide, 1,4-cyclohexanedicarboxylic acid bis(2-methylcyclohexylamide), 1,4 -Cyclohexanedicarboxylic acid dibenzylamide, 2,6-naphthalene dicarboxylic acid dicyclohexylamide, 1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide, 1,2,3,4 - Compounds such as butane tetracarboxylic acid tetrabenzamide.

The particle size of the amide compound used in the present invention is not particularly limited as long as the effect of the present invention can be obtained, but considering the dissolution rate or dispersibility of the molten resin, the particle size should be as small as possible, usually measured by laser diffraction method The average particle size is 0.1-500 μm, preferably 1-200 μm, more preferably 1-100 μm.

Ester plasticizer

The ester-based plasticizer used in the present invention is not particularly limited, but it is preferable to use (1) polyhydric alcohol derivatives, (2) hydroxycarboxylic acid derivatives, (3) aliphatic or aromatic carboxylic acid esters , (4) polyether polyol derivatives, (5) phosphoric acid derivatives, etc., particularly preferred are (1) polyol derivatives, (2) hydroxycarboxylic acid derivatives, and (4) polyether polyol derivatives. These can be used individually or in combination of 2 or more types.

(1) Polyol derivatives

As the polyhydric alcohol derivative, glycerol derivatives are preferred.

Examples of glycerol derivatives include glycerol trialiphatic carboxylic acid (aliphatic carboxylic acid: 2 to 18 carbon atoms) esters, specifically glycerol triacetate, glycerol tripropionate, Glycerol tricaproate, glycerol tricaprylate, glycerol tri(2-ethylhexanoate), glycerol triisononanoate, glycerol triisostearate, etc.

(2) Hydroxycarboxylic acid derivatives

As hydroxycarboxylic acid derivatives, preferably citric acid derivatives, specifically acetyl citrate trialkyl (alkyl: 1 to 18 carbon atoms) ester, and citrate trialkyl (alkyl: 1 to 18 carbon atoms) ester. Examples of these typical examples include acetyl triethyl citrate, acetyl triisopropyl citrate, acetyl citric acid trialkyl (alkyl: 1 to 18 carbon atoms) acetyl citrate, Tributyl Citrate, Tris(2-Ethylhexyl) Acetyl Citrate, Triisononyl Acetyl Citrate, Triisostearyl Acetyl Citrate, Triethyl Citrate, Triisopropyl Citrate, Tributyl citrate, tris(2-ethylhexyl) citrate, triisononyl citrate, triisostearyl citrate, etc.

(4) Polyether polyol derivatives

As the polyether polyol derivatives, polyalkylene glycol derivatives are preferable. Examples of the polyalkylene glycol derivatives include polyalkylene glycol and aliphatic carboxylic acids having 2 to 18 carbon atoms, preferably 6 to 10 carbon atoms, and aliphatic carboxylic acids having 7 to 18 carbon atoms, preferably 7 to 10 carbon atoms. Diesters of 14 aromatic carboxylic acids, etc.

As the aromatic carboxylic acid, benzoic acid having 1 to 2 (especially 1) substituents selected from C1 to C4 alkyl groups, halogen atoms, phenyl groups, and hydroxyl groups may be used. The benzoic acid is more preferred.

Examples of the above-mentioned polyalkylene glycol include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (number average molecular weight = 150 to 2000), dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol ( Number average molecular weight=150～2000) etc.

Examples of these esters include diethylene glycol dialiphatic carboxylic acid (aliphatic carboxylic acid: 2 to 18 carbon atoms) ester, triethylene glycol dialiphatic carboxylic acid (aliphatic carboxylic acid: 2 to 18 carbon atoms), ) ester, tetraethylene glycol dialiphatic carboxylic acid (aliphatic carboxylic acid: 2 to 18 carbon atoms) ester, polyethylene glycol (number average molecular weight = 150 to 2000) dialiphatic carboxylic acid (aliphatic carboxylic acid: C2-18) ester, diethylene glycol diaromatic carboxylate, triethylene glycol diaromatic carboxylate, tetraethylene glycol diaromatic carboxylate, polyethylene glycol (number average molecular weight=150～ 2000) diaromatic carboxylic acid ester, dipropylene glycol dialiphatic carboxylic acid (aliphatic carboxylic acid: carbon number 2 to 18) ester, tripropylene glycol dialiphatic carboxylic acid (aliphatic carboxylic acid: carbon number 2 to 18) ) ester, tetrapropylene glycol dialiphatic carboxylic acid (aliphatic carboxylic acid: carbon number 2 to 18) ester, polypropylene glycol (number average molecular weight = 150 to 2000) dialiphatic carboxylic acid (aliphatic carboxylic acid: carbon number 2~18) Esters, Dipropylene Glycol Diaromatic Carboxylate, Tripropylene Glycol Diaromatic Carboxylate, Tetrapropylene Glycol Diaromatic Carboxylate, Polypropylene Glycol (Number Average Molecular Weight=150~2000) Diaromatic Carboxylate wait.

Specific examples of polyalkylene glycol derivatives include diethylene glycol diacetate, diethylene glycol dipropionate, diethylene glycol dicaproate, diethylene glycol dicaprylate, diethylene glycol Di(2-ethylhexanoate), diethylene glycol diisononanoate, diethylene glycol diisostearate, triethylene glycol diacetate, triethylene glycol dipropionate, triethylene glycol dihexyl Triethylene glycol dicaprylate, Triethylene glycol bis(2-ethylhexanoate), Triethylene glycol diisononanoate, Triethylene glycol diisostearate, Tetraethylene glycol diacetate , tetraethylene glycol dipropionate, tetraethylene glycol dicaproate, tetraethylene glycol dicaprylate, tetraethylene glycol di(2-ethylhexanoate) ester, tetraethylene glycol diisononanoate, tetraethylene glycol Alcohol diisostearate, polyethylene glycol diacetate, polyethylene glycol dipropionate, polyethylene glycol dicaproate, polyethylene glycol dicaprylate, polyethylene glycol di(2 -ethylhexanoate), polyethylene glycol diisononanoate, polyethylene glycol diisostearate, diethylene glycol dibenzoate, diethylene glycol dicresylate, diethylene glycol di (ethylparaben), diethylene glycol bis(isopropyl benzoate), diethylene glycol bis(tert-butyl benzoate), diethylene glycol bis(chlorobenzoate), diethylene glycol bis(chlorobenzoate), Glycol bis(hydroxybenzoate), Diethylene glycol bis(phenyl benzoate), Triethylene glycol dibenzoate, Triethylene glycol dicresate, Triethylene glycol bis(ethyl benzoate) ester), triethylene glycol bis(isopropyl benzoate), triethylene glycol bis(tert-butyl benzoate), triethylene glycol bis(chlorobenzoate), triethylene glycol bis(hydroxy benzoate), triethylene glycol bis(phenyl benzoate), tetraethylene glycol dibenzoate, tetraethylene glycol dicresinate, tetraethylene glycol bis(ethyl benzoate), tetraethylene glycol dibenzoate Tetraethylene glycol bis(isopropyl benzoate), tetraethylene glycol bis(tert-butyl benzoate), tetraethylene glycol bis(chlorobenzoate), tetraethylene glycol bis(hydroxybenzoate) , Tetraethylene glycol bis(phenyl benzoate), polyethylene glycol dibenzoate, polyethylene glycol ditoluate, polyethylene glycol bis(ethyl benzoate), polyethylene glycol dibenzoate Alcohol bis(isopropyl benzoate), macrogol bis(tert-butyl benzoate), macrogol bis(chlorobenzoate), macrogol bis(hydroxybenzoate) ester), polyethylene glycol bis(phenyl benzoate), dipropylene glycol dipropyl acetate, dipropylene glycol dipropionate, dipropylene glycol dicaproate, dipropylene glycol dicaprylate, dipropylene glycol di(2 -ethylhexanoate), dipropylene glycol dinonyl carboxylate, dipropylene glycol diisostearate, tripropylene glycol dipropyl acetate, tripropylene glycol dipropionate, tripropylene glycol dicaproate, tripropylene glycol di Caprylate, Tripropylene Glycol Di(2-Ethylhexanoate), Tripropylene Glycol Dinonate, Tripropylene Glycol Distearate, Tetrapropylene Glycol Diacetate, Tetrapropylene Glycol Dipropionate, Tetrapropylene Glycol Dihexanoate tetrapropylene glycol dicaprylate, tetrapropylene glycol di(2-ethylhexanoate), tetrapropylene glycol diisononanoate, tetrapropylene glycol diisostearate, polypropylene glycol diacetate, polypropylene glycol diacetate Propionate, Polypropylene Glycol Dicaproate, Polypropylene Glycol Dicaprylate, Polypropylene Glycol Di(2-Ethylhexanoate), Polypropylene Glycol Diisononanoate, Polypropylene Glycol Diisostearate, Dipropylene Glycol Dibenzoate, Dipropylene Glycol Dimethylbenzoate, Dipropylene Glycol Bis(Ethyl Benzoate), Dipropylene Glycol Bis(Isopropyl Paraben), Dipropylene Glycol Bis(tert-Butyl Benzoate) , Dipropylene Glycol Bis(Chlorobenzoate), Dipropylene Glycol Bis(Hydroxybenzoate), Dipropylene Glycol Bis(Phenylbenzoate), Tripropylene Glycol Dibenzoate, Tripropylene Glycol Dimethylbenzoate, Tripropylene Glycol Bis(Ethyl Benzoate), Tripropylene Glycol Bis(Isopropyl Benzoate), Tripropylene Glycol Bis(tert-Butyl Benzoate), Tripropylene Glycol Bis(Chlorobenzoate), Tripropylene Glycol Bis(Chlorobenzoate), Propylene Glycol Bis(Hydroxybenzoate), Tripropylene Glycol Bis(Phenyl Benzoate), Tetrapropylene Glycol Dibenzoate, Tetrapropylene Glycol Dimethylbenzoate, Tetrapropylene Glycol Bis(Ethyl Benzoate), Tetrapropylene Glycol Bis(Ethyl Benzoate), Propylene Glycol Di(isopropyl benzoate), Tetrapropylene Glycol Di(tert-butyl benzoate), Tetrapropylene Glycol Di(chlorobenzoate), Tetrapropylene Glycol Di(hydroxybenzoate), Tetrapropylene Glycol Di(tert-butyl benzoate), Tetrapropylene Glycol Di(hydroxybenzoate), (Phenyl Benzoate), Polypropylene Glycol Dibenzoate, Polypropylene Glycol Ditoluate, Polypropylene Glycol Di(Ethyl Benzoate), Polypropylene Glycol Di(Isopropyl Benzoate), Polypropylene glycol bis(tert-butyl benzoate), polypropylene glycol bis(chlorobenzoate), polypropylene glycol bis(hydroxybenzoate), polypropylene glycol bis(phenyl benzoate), etc.

(3) Aliphatic acid or aromatic carboxylic acid ester

Examples of aliphatic acids or aromatic carboxylic acid esters include monocarboxylic acid esters such as butyl oleate and butyl isostearate, di-2-ethylhexyl phthalate, diisophthalic acid Phthalate esters (monoester or diester) such as nonyl ester, for example, adipate esters (monoester or diester) such as isobutyl adipate and di-2-ethylhexyl adipate , The same ester (monoester or diester) of sebacic acid and azelaic acid is used instead of adipic acid.

(5) Phosphoric acid derivatives

Examples of phosphoric acid derivatives include tris(C1-C12 alkyl) phosphate and tris(C6-C12 aryl) phosphate, such as tributyl phosphate, tri-2-ethylhexyl phosphate, phosphoric acid Triphenyl ester, tricresyl phosphate, etc.

Lactic acid polymer

Lactic acid-based polymers as the main component of the present invention include (a) lactic acid homopolymers, (b) lactic acid copolymers, and (c) at least one selected from the constituent groups of lactic acid homopolymers and lactic acid copolymers. A mixed polymer or the like in which another polymer is mixed in one type. The lactic acid component used as a raw material for these lactic acid-based polymers is not particularly limited, but L-lactic acid, D-lactic acid, or a mixture thereof, or L-lactide and D-lactide of a cyclic dimer of lactic acid can be used. , meso-lactide or mixtures of these.

As lactic acid, the ratio (L/D) of the L-form and the D-form is not particularly limited, but in order to obtain a high melting point, it is desirable to have high optical purity. Specifically, as lactic acid, it is preferable that the L-form accounts for 80 mol% or more, and more preferably 95 mol% or more of the whole lactic acid. In addition, for lactide, the L-form accounts for preferably 80 mol% or more, and more preferably 95 mol% or more, of the whole lactide. In such lactic acid-based polymers, the weight-average molecular weight of the lactic acid homopolymer and lactic acid copolymer is not particularly limited, and can be selected within a wide range, but it is preferably 50,000 or more, and more preferably 50,000 to 50,000. 500,000, most preferably 100,000 to 500,000.

(Lactic Acid Homopolymer)

As the lactic acid homopolymer used in the present invention, direct dehydration condensation of L-lactic acid, D-lactic acid, DL-lactic acid or a mixture of these, or direct dehydration condensation of L-lactide, D-lactide, meso-lactide, etc. A polymer obtained by ring-opening polymerization of lactide, a cyclic dimer of lactic acid.

(lactic acid copolymer)

Lactic acid copolymers are random or block copolymers of the aforementioned lactic acid monomers, lactides or lactic acid homopolymers and other copolymerizable components. At this time, the lactic acid homopolymer used for the production of the copolymer can be used in a wide range, but it is desirable to use a weight average molecular weight of about 1,000 to 200,000, preferably about 5,000 to 100,000.

The above-mentioned other components that can be copolymerized include, for example, compounds having two or more ester bond functional groups in the molecule, such as a) dicarboxylic acids, b) polyols, c) hydroxycarboxylic acids other than lactic acid, d) lactones, etc., and e) various polyesters, polyethers, and carbonates composed of these components.

a) As the above-mentioned dicarboxylic acid, specifically, straight-chain or branched saturated or unsaturated aliphatic dicarboxylic acids with 4 to 50 carbon atoms, especially 4 to 20 carbon atoms, aromatic 8 to 20 20 aromatic dicarboxylic acids, and polyether dicarboxylic acids with a number average molecular weight of 2000 or less, especially 1000 or less. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, sebacic acid, sebacic acid, and other straight-chain aliphatic dicarboxylic acids having 4 to 20 carbon atoms, and examples of the aromatic dicarboxylic acid include Phthalic acid, terephthalic acid, isophthalic acid, etc.

Examples of the polyether dicarboxylic acid include polyalkylene ethers such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol, polyethylene polypropylene glycol, etc., having carboxymethyl dicarboxylic acid at both ends. acid. Among these, polyether dicarboxylic acids having a number average molecular weight of 2,000 or less, more preferably 1,000 or less, and most preferably 178 to 1,000 are preferred.

b) Examples of the aforementioned polyhydric alcohols include aliphatic polyhydric alcohols, aromatic polyhydric alcohols, and polyalkylene ethers. Aliphatic polyols. Examples thereof include butanediol and hexanediol. Caprylyl glycol, decanediol, 1,4-cyclohexanedimethanol, glycerol, sorbitan, trimethylolpropane, neopentyl glycol, etc. have 2 to 4 carbon atoms in hydroxyl groups 2-50, especially 2-20 aliphatic polyols.

Examples of aromatic polyhydric alcohols include bis(o-, m-, or p-)hydroxymethylbenzene, aromatic diols having 6 to 20 carbon atoms such as hydroquinone, bisphenol A, and bisphenol F. Add ethylene oxide, propylene oxide, and butylene oxide to bisphenols such as bisphenols to obtain aromatic diols with a number average molecular weight of 2000 or less, especially aromatic diols with a number average molecular weight of less than 1000.

Examples of polyalkylene ethers include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, etc., having a number average molecular weight of 2,000 or less, especially ether alcohols having a number average molecular weight of 1,000 or less. .

c) Hydroxycarboxylic acids other than lactic acid include hydroxycarboxylic acids having 3 to 10 carbon atoms such as glycolic acid, hydroxybutylcarboxylic acid, and 6-hydroxycaproic acid (excluding lactic acid).

d) Lactones include glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone , valerolactone, δ-valerolactone, etc.

e) As various polyesters, various polyethers, and various polycarbonates, as long as they are conventionally used in the production of lactic acid-based polymers, they can be used without particular limitation, and these weight average molecular weights are preferably 1,000 to 150,000 , the range of 5,000 to 100,000 is recommended.

Among the above-mentioned various polyesters, various polyethers, and various polycarbonates, it is particularly preferable to use polyester as a copolymer, and as the polyester of these copolymers, aliphatic dicarboxylic acid (e- 1) Aliphatic polyester composed of aliphatic diol (e-2).

The aliphatic dicarboxylic acid (e-1) that is one of the constituent components of the above-mentioned aliphatic carboxylic acid polyester includes 4 carbon atoms such as succinic acid, adipic acid, sebacic acid, and sebacic acid. ~20 linear aliphatic dicarboxylic acids, but those with double bonds in the side chains can be used.

The aliphatic diol (e-2) which is one component of the above-mentioned aliphatic carboxylic acid polyester includes aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and octane glycol. And polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyalkylene ether (single copolymer or copolymer) and polyalkylene carbonate. The polyalkylene ether and polyalkylene carbonate preferably have a number average molecular weight of 2,000 or less, particularly preferably 1,000 or less.

In addition to aliphatic dicarboxylic acids and aliphatic diols, as auxiliary components, as long as they contain hydroxycarboxylic acids such as lactic acid, glycolic acid, and hydroxybutylcarboxylic acid, butyrolactone, ε-caprolactone, etc. Compounds having ester bond-forming functional groups such as esters and aromatic dicarboxylic acids can be used as constituents of the aliphatic polyester as long as they do not impair the effects of the present invention. Among the above-mentioned lactic acid copolymers, a copolymer of lactic acid and the hydroxycarboxylic acid (excluding lactic acid) of c) above, a lactic acid/diol/dicarboxylic acid copolymer (particularly lactic acid and the above-mentioned aliphatic diol (e-2) and the above-mentioned aliphatic dicarboxylic acid (e-1)), a copolymer of lactic acid and the above-mentioned lactone in d).

In the lactic acid polymer used in the present invention, the copolymerization components a) to e) are preferably less than 50% by mass of the total weight of the lactic acid-based polymer mainly composed of lactic acid. The more the amount of the copolymer components a) to e), the more the crystallinity and heat resistance of the lactic acid polymer tend to decrease, so it should be selected according to the ratio of the copolymer component and the application, but for the lactic acid polymer The total weight of is preferably 1 to 30% by weight, more preferably 5 to 20% by weight.

(hybrid polymer)

The mixed polymer is at least one selected from the group consisting of the above-mentioned lactic acid homopolymer and lactic acid copolymer as a main component, and further contains, as other polymer, polyester, for example, aliphatic polyester, aromatic poly Esters or complexes of these mixtures. Other polymers are preferably aliphatic polyesters from the standpoint of biodegradability.

The blending ratio of other polymers can be appropriately selected according to the purpose and use, but for 95 to 50% by weight of at least one selected from the above-mentioned lactic acid homopolymer and lactic acid copolymer constituting group, the polyester is 5 to 50% by weight. 50% by weight range. When the amount of polyester is less than 5% by weight, it is difficult to obtain flexibility and impact resistance, and when it exceeds 50% by weight, mechanical and physical properties are insufficient, and transparency is difficult to obtain. 94 to 60% by weight of at least one selected from the group consisting of the above-mentioned lactic acid homopolymer and lactic acid copolymer is not preferable, and the polyester is in the range of 6 to 40% by weight.

If the molecular weight of the polyester in the mixed polymer is too low, it is not desirable that the mechanical physical properties are insufficient. As the polyester, the weight average molecular weight is preferably 10,000 or more, more preferably 30,000 or more, most preferably 50,000 or more, and usually 50,000 to 300,000 are most widely used.

Examples of aliphatic dicarboxylic acids that are constituents of aliphatic polyesters include straight-chain aliphatic dicarboxylic acids having 4 to 20 carbon atoms such as succinic acid, adipic acid, sebacic acid, and dodecyl dicarboxylic acid. Dicarboxylic acids, but those with side chains or double bonds can also be used.

The aliphatic diols that are constituents of aliphatic polyesters include aliphatic diols and polyols having 2 to 20 carbon atoms such as ethylene glycol, propylene glycol, butanediol, hexylene glycol, and octanediol. Polyalkylene ethers (individual polymers or copolymers) of ethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., and polyalkylene carbonates. The polyalkylene ether and polyalkylene carbonate preferably have a number average molecular weight of 2,000 or less, especially 1,000 or less.

In addition to aliphatic dicarboxylic acids and aliphatic diols, as auxiliary components, as long as they contain hydroxycarboxylic acids such as lactic acid, glycolic acid, and hydroxybutylcarboxylic acid, butyrolactone, ε-caprolactone, etc. Compounds having ester bond-forming functional groups such as esters and aromatic dicarboxylic acids can be used as constituents of the aliphatic polyester as long as they do not impair the effects of the present invention.

(Manufacturing method of lactic acid polymer)

As the lactic acid polymer of the present invention, it can be manufactured by conventionally known methods, and the specific lactic acid homopolymer can be manufactured from the direct dehydration polymerization of lactic acid monomer, or the open-ended polymerization of lactic acid cyclic dimer lactide ( For example, JP-A-7-33861 and JP-A-59-96123).

The synthesis, purification and polymerization of lactide are described, for example, in US Pat. 1986) et al.

As the lactic acid-based polymer, when using a copolymer of lactic acid and the hydroxycarboxylic acid of c) above or a copolymer of lactic acid and the lactone of d) above, the method for producing the polymer includes lactic acid and the hydroxyl group of c) above. A production method of direct dehydration polycondensation of carboxylic acid or a method of ring-opening polymerization of a cyclic dimer of lactic acid (lactide) and a lactone of the above-mentioned d) under suitably using an aliphatic metal salt such as a catalyst tin dihexanoate ( For example, JP-A-6-306264 and U.S. Patent No. 4,057,537 are described).

As a lactic acid-based polymer, when using a lactic acid/diol/dicarboxylic acid copolymer, the method for producing the polymer includes cyclic dimers of lactic acid and aliphatic compounds with various compositional ratios in the presence of an open catalyst. A method of reacting a polyester polymer composed of dicarboxylic acid (e-1) and diol (e-2) (for example, JP-A-7-173266). A method of reacting (i) a lactic acid homopolymer, (ii) a polyester composed of an aliphatic diol (e-2) and an aliphatic dicarboxylic acid (e-1) in the presence of an organic solvent (e.g. , EP0712880 A2 bulletin).

In addition, the mixed polymer used in the present invention is obtained by mixing at least one selected from the group consisting of the above-mentioned lactic acid homopolymer and lactic acid copolymer with the above-mentioned other polymer according to a conventional method. The mixing method is not particularly limited, and for example, conventionally known methods of mixing by mechanical stirring in a molten state or a solution state, mixing in a powder state or a granular state, and then melting or dissolving can be used. Specifically, the above hybrid polymer is produced using an extruder, a reactor, a roll, or the like.

Lactic acid polymer composition

The lactic acid-based polymer composition of the present invention contains the aforementioned amide-based mixture, an ester-based plasticizer, a lactic acid-based polymer, and other additives as necessary.

The amount of the amide compound added is 0.01 to 10 parts by weight, preferably 0.05 to 15 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the lactic acid polymer. When it is less than 0.01 parts by weight, the effect as a transparent nucleating agent is not sufficient. On the contrary, when it exceeds 10 parts by weight, a part of the amide compound remains in an undissolved state in the molten resin, or aggregates, so the transparency of the molded product is reduced. Sexual deterioration. These amide compounds can be used alone or in combination of two or more.

The amount of the ester plasticizer added is 1 to 300 parts by weight, preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, based on 100 parts by weight of the lactic acid polymer. When the content is less than 1 part by weight, the effect as a crystallization accelerator is insufficient. Conversely, when it exceeds 300 parts by weight, the plasticizer is precipitated on the surface of the obtained molded body, which tends to deteriorate over time. In addition, the ester-based plasticizer blended in the lactic acid-based polymer can usually be used alone, but two or more kinds can also be used in combination if necessary.

The method of blending the amide compound and the ester plasticizer into the lactic acid polymer is not particularly limited, and conventional methods known in the art can be used, for example, using a Henschel mixer, a ribbon mixer, an extruder , a reactor, a kneader, a roll, and a combination of these, etc., to mix the respective raw materials in a solid state, or to further melt-mix and knead the polymer. These kneading is usually carried out at a temperature of 120 to 250°C, preferably at a temperature of 150 to 200°C. The obtained lactic acid-based polymer composition of the present invention is usually in the form of pellets.

Furthermore, in the lactic acid-based polymer composition of the present invention, in order to improve various physical properties such as crystallization rate, heat resistance, mechanical properties, and blocking resistance, you may add Inorganic additives for talc, kaolin, SiO ₂ , clay, etc. For example, i) for the purpose of improving crack resistance, SiO ₂ or the like having a particle diameter of 1 to 50 nm that does not impair transparency may be added. ii) For the purpose of further increasing the crystallization rate during molding, a crystalline inorganic substance containing 10% by weight or more of SiO ₂ may be used. Specific examples of such inorganic substances include talc TM-30 (manufactured by Fuji Talc Co., Ltd.), kaolin JP100 (manufactured by Tsuchiya Kaolin Co., Ltd.), NN kaolin clay (manufactured by Tsuchiya Kaolin Co., Ltd.), kaolinite ASP-170 (manufactured by Fuji Talc Co., Ltd. ), kaolin UV (manufactured by Engelhard Co.), talc RF (manufactured by Fuji Talc Co., Ltd.), etc.

The amount of these inorganic additives added is not particularly limited within the range that does not affect the transparency of the molded article, but it is 30 parts by weight or less with respect to 100 parts by weight of the lactic acid polymer, preferably 20 parts by weight or less, more preferably It is 10 parts by weight or less, most preferably 1 part by weight or less. Furthermore, as other additives, pigments, stabilizers, antistatic agents, ultraviolet absorbers, antioxidants, flame retardants, release agents, Lubricants, dyes, antibacterial agents, various elastomers, various fillers, etc.

Shaped body of the invention

The molded article obtained by molding the thus obtained lactic acid-based polymer composition of the present invention has good productivity and excellent transparency and crystallinity (heat resistance).

As the molding method, various methods such as extrusion molding, injection molding, vacuum molding, and pressure molding, which are common to plastics, can be used without any particular limitation.

(crystallization)

When molding the lactic acid polymer composition or after molding, as a method of crystallizing the molded body, for example, at the time of molding, 1) filling the melt of the composition in a metal mold, and directly crystallizing it in the metal mold 2) extruding the melt of the composition from a T-die extrusion molding machine, and crystallizing it on a hard-faced roll (hereinafter, 1) and 2) are referred to as "one-stage crystallization method") , and 3) a method of heat-treating the obtained amorphous or partially crystallized molded body after molding the composition (hereinafter referred to as "two-stage crystallization method"). The optimum temperature conditions for crystallizing a molded body differ between the one-stage crystallization method and the two-stage crystallization method.

The temperature condition for crystallization in the one-stage crystallization method is preferably crystallization of the lactic acid-based polymer composition in differential scanning calorimetry (hereinafter, abbreviated as "DSC analysis") of the lactic acid-based polymer composition (particles). The range from the onset temperature (hereinafter abbreviated as "Tc") to the glass transition temperature (hereinafter abbreviated as "Tg") of the lactic acid-based polymer composition. At a temperature higher than Tc, the crystallization rate is significantly reduced, and productivity and operability are deteriorated, and crystallization cannot be performed, and the desired molded product may not be obtained. On the contrary, at a temperature lower than Tg, the crystallization rate is lower. Remarkably smaller, productivity and handleability deteriorate, further crystallization is not possible, and the desired molded product may not be obtained. Conversely, when the temperature is lower than the Tg temperature, the crystallization rate becomes significantly smaller, and the desired molded product may not be obtained. In this method, the retention time of crystallization varies depending on the lactic acid-based polymer composition, but the molded article is not limited as long as the crystallization time is sufficient.

In addition, when the two-stage crystallization method is used, the temperature conditions are set, preferably within the temperature range from the melting point (hereinafter, abbreviated as "Tm") to Tg of the lactic acid-based polymer composition (particles), more preferably (Tg+ 5°C) to (Tm-20°C), more preferably (Tg+10°C) to (Tm-40°C). When the set temperature is higher than Tm, even if it crystallizes in a short time, the transparency may be lost and the shape may be strained, and further, when heated for a long time, melting may occur. Conversely, at a temperature lower than Tg, the crystallization rate is remarkably low, and the desired molded product may not be obtained. In this method, the time for heat-treating the molded body varies depending on the composition, but there is no limitation as long as the molded body has sufficient crystallization time.

However, compared with the one-stage crystallization method, the two-stage crystallization method is not necessarily industrially preferable because the molding cycle speed is slower.

From the lactic acid-based polymer composition of the present invention, it goes without saying that a molded article with high transparency and crystallinity can be obtained by the one-stage crystallization method with excellent molding cycle by the above-mentioned two-stage crystallization method.

In the crystallization mechanism estimated in the present invention, when the molten lactic acid polymer composition is cooled, the amide compound acts as a crystallization nucleus in the lactic acid polymer composition, and due to the crystallization of the lactic acid polymer, Since it becomes a small crystal, a molded product with high transparency and crystallinity can be obtained, and it is presumed that the amide compound functions as a crystal nucleus. In addition, ester-based plasticizers have a function of increasing crystallization, especially increasing the crystallization rate of lactic acid-based polymers, and are presumed to shorten the cycle time of moldings.

In addition, in this specification, Tg and Tm are expressed as the point when the composition becomes rubbery when the temperature of the lactic acid-based polymer composition (=particles) is raised under the condition of 10° C./min in the DSC analysis. The glass transition temperature (Tg), the apex temperature of the melting peak of the lactic acid-based polymer composition (melting point: Tm), and Tc are indicated. In DSC analysis, the molten product of the lactic acid-based polymer composition is heated at 10°C/min. The crystallization initiation temperature (Tc) of the lactic acid-based polymer composition when cooled under certain conditions.

Hereinafter, a typical production method of a molded article that imparts both transparency and crystallinity to the molded article of the present invention will be described.

For example, during a) injection molding, the melt of the lactic acid polymer composition (pellets) to which the amide compound, the ester plasticizer and the lactic acid polymer are added is added to a temperature range of Tc to Tg. Holding in a metal mold, a molded article having both transparency and crystallinity, which is the object of the present invention, can be obtained by a one-stage production method. In addition, for example, the molten material of the above-mentioned pellets is filled in a metal mold kept at a temperature lower than Tg, and the obtained amorphous or partially crystallized molded product is kept in an atmosphere within a temperature range from Tg to Tm, or The molded article which is the object of the present invention and which has both transparency and crystallinity can also be obtained by contacting with an appropriate heat medium by a two-stage production method.

b) During extrusion molding, for example, extrude the molten material of the above-mentioned particles into a chilled roll kept in the temperature range of Tc～Tg with a general T-die extruder, and crystallize on the chilled roll, A sheet or film having both transparency and crystallinity, which is the object of the present invention, can be obtained by a one-stage production method. In addition, for example, the film or sheet is heat-treated in an oven (furnace) kept in the range of Tg to Tm or in hot water continuously or in batches, and the present invention can be obtained by a two-stage production method. As the objective sheet or film having both transparency and crystallinity, the film or sheet is made by extruding the above-mentioned particles into a chilled roll maintained at a temperature lower than Tg using a general T-die extrusion molding machine. A crystalline or partially crystalline film or sheet.

The lactic acid-based polymer molded article of the present invention has excellent transparency. As an index of transparency, the haze of the molded article having a thickness of 0.5 mm is 70% or less, preferably 50% or less, and particularly preferably 30%. the following. In addition, the lactic acid-based polymer molded article has high crystallinity in addition to the above-mentioned high transparency. As an indicator of crystallinity, the degree of crystallinity measured by an X-ray diffractometer is 30% or more, which is particularly preferable. is more than 40%. By the above production method, a molded body having a crystallinity of 30% or more, a thickness of 0.5 mm or less, and a haze of 70% or less can be easily obtained. Furthermore, if an appropriate temperature condition for crystallization is selected among the above-mentioned molding conditions, it is also possible to obtain a lactic acid-based polymer molded with transparency and crystallinity (heat resistance) having a haze of 30% or less when the thickness is less than 0.5mm. body.

Thus, the present invention is to provide a lactic acid-based polymer molded article, which is composed of the above-mentioned lactic acid-based polymer composition of the present invention (that is, the above-mentioned amide compound, the above-mentioned ester-based plasticizer, and the above-mentioned lactic acid-based polymer and optionally containing Composition of other additives) composition, the crystallinity of the present invention is 30% or more, and when the thickness is 0.5 mm or less, the haze is 70% or less, preferably 50% or less, particularly preferably 30% or less.

Films, sheets, tapes, labels, laminations, fibers, braids, fabrics, non-woven fabrics, etc. Woven cloth, paper, felt, bags, tubes, porous molded products, various containers, various parts, and other molded products. Specifically, the molded product of the present invention is an agricultural and aquatic industry, horticultural material, Containers for food utensils, food packaging films, trays, stretch films, shrink films, beverage bottles, etc. Food packaging materials, heat insulating materials, molds, soil protection films, water retention films, soil bags, etc. Civil engineering and construction materials, Hygienic materials such as disposable diapers and sanitary product packaging, food bags, microwave bags, garbage bags, general size bags, sheets, tapes, labels, shampoo bottles, rinse bottles, cosmetic containers, etc. Daily miscellaneous goods, packaging materials, Industrial materials such as cushioning materials, binding tapes, ropes, housing materials for home appliances and OA, automotive parts, etc.

Example

Hereinafter, the present invention will be described using production examples, examples, and comparative examples, but the present invention is not limited thereto. In addition, "part" in an example shows a weight standard. In addition, the evaluation conditions of the physical properties of the molded article obtained from the melting point of the amide-based compound and the lactic acid-based polymer composition of the present invention are as follows.

1) Melting point of amide compound

The temperature of the endothermic peak (peak apex) confirmed when the temperature of the amide compound was raised at 10° C./min using a differential scanning calorimetry apparatus (manufactured by Shimadzu Corporation, DSC-50) was defined as the melting point.

2) Transparency (haze)

According to JIS K-6714, the measurement was performed using a haze meter (Haze Meter) manufactured by Toyo Seiki Seisakusho.

3) Crystallinity

Using an X-ray diffractometer (manufactured by Rigaku Corporation, RINT-2100 type), the molded test piece was measured at 2θ in the range of 12° to 28°, and the crystallization peak area to the total area (crystallization portion) of the obtained recording paper was calculated. and the total area of the amorphous part) ratio.

4) Tensile test

Yield strength and elongation were measured according to JIS K-6723.

5) Heat resistance test

The test piece was placed in an 80° C. Gill aging incubator, and the deformation state of the test piece after 24 hours was visually judged and evaluated in the following three stages.

○: No deformation can be seen

△: Slight deformation is seen

×: Obvious deformation is seen

6) Crystallization start temperature (Tc)

Once the lactic acid-based polymer composition (pellets obtained in the following Examples and Comparative Examples) was melted using a differential scanning calorimeter (manufactured by PerkinElmer, DSC7), the temperature was lowered at 10°C/min. , the temperature at which the crystallization peak of the lactic acid-based polymer composition was observed was defined as the crystallization initiation temperature (Tc).

7) Glass transition temperature (Tg) and melting point (Tm)

When using a differential scanning calorimeter (manufactured by PerkinElmer, DSC7) to raise the temperature of the lactic acid-based polymer composition (particles obtained in the following Examples and Comparative Examples) at 10° C./min, The point at which the lactic acid-based polymer composition changed into a rubbery state was defined as the glass transition point (Tg), and the apex of the melting peak of the lactic acid-based polymer composition was defined as the melting point (Tm).

Manufacturing example 1

In a 0.5L flask equipped with a stirrer, a thermometer, a reflux cooler and a nitrogen inlet tube, add 0.03 mole of trimesic acid, 0.099 mole of cyclohexylamine, 0.099 mole of triphenyl phosphite, 10 g of pyridine and 50 g of N-methylpyrrolidone , reacted at 100° C. for 4 hours under nitrogen atmosphere. After cooling to room temperature, it was added to 500 ml of an equal volume mixture of isopropanol/water for reprecipitation. Next, filtration and drying were performed to obtain the target trimesic acid tricyclohexylamide. As a result of FT-IR analysis, it was confirmed that the absorption of the carboxyl group disappeared, and from the observation of the absorption of the amide group (1633 cm-1), it was confirmed that trimesic acid tricyclohexylamide was generated. The melting point is 384°C.

Examples 1-23

For 100 parts by weight of polylactic acid (weight-average molecular weight: 180,000, L-lactic acid/D-lactic acid=97/3, manufactured by Shimadzu Corporation, trade name "Lacute"), the ingredients listed in Table 1 were quantitatively mixed according to regulations. The amide compound and the ester plasticizer described above were used in an extruder with a barrel inner diameter of 20 mm (length/diameter ratio = 19, manufactured by Toyo Seiki Seisakusho Co., Ltd., with a trade name of "LaboPlastomil". )"), kneading at 200°C, cooling the resin composition extruded by nitrogen purge with water, and then granulating it with a granulator. The obtained pellets were vacuum-dried at 50° C. for 24 hours before molding and used.

Next, the dried pellets were sandwiched between a press set at 200°C and melted for 2 minutes, and then pressed at 200°C under a pressure of 100kgf/ ^cm2 for 5 minutes, and then crystallized under the conditions described in Table 1. A sheet with a thickness of 0.5 mm was obtained by one-stage crystallization.

From the obtained sheet, a test piece (thickness = 0.5 mm) was cut out, and the transparency (haze), crystallinity, tensile test, and heat resistance test of the test piece were measured. The results are shown in Table 1 and Table 2.

Comparative example 1-5

Pellets were produced in the same manner as in Example 1 except that no amide compound was added. The pellets obtained were dried, molded in the same manner as in Examples, and crystallized under the conditions shown in Table 2 to obtain a sheet with a thickness of 0.5 mm. Table 2 shows the measurement results of physical properties of the obtained sheet.

Comparative Examples 6-7

Pellets were produced in the same manner as in Example 1 except that no ester-based plasticizer was added. The pellets obtained were dried, molded in the same manner as in Examples, and crystallized under the conditions shown in Table 2 to obtain a sheet with a thickness of 0.5 mm. Table 2 shows the measurement results of physical properties of the obtained sheet.

Comparative Examples 8-9

Pellets were produced in the same manner as in Example 1 except that no amide compound and ester plasticizer were added. The pellets obtained were dried, molded in the same manner as in Examples, and crystallized under the conditions shown in Table 2 to obtain a sheet with a thickness of 0.5 mm. Table 2 shows the measurement results of physical properties of the obtained sheet.

Examples 24-26

For 100 parts by weight of polylactic acid (weight-average molecular weight: 180,000, L-lactic acid/D-lactic acid = 97/3, manufactured by Shimadzu Corporation, trade name "Lacourt"), quantitatively mix the amide compounds described in Table 3 and an ester-based plasticizer, using an extruder with a barrel inner diameter of 20 mm (length/diameter ratio = 19, manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name "Plaster Mill"), kneading at 200°C , the resin composition extruded by nitrogen purging was cooled with water and then granulated with a granulator. The obtained pellets were vacuum-dried at 50° C. for 24 hours before molding and used.

Next, the above-mentioned dry pellets were extruded in an extrusion molding machine (mold clamping pressure 40 tons, manufactured by Nissei Plastic Industry Co., Ltd.) at a cylinder temperature of 160 to 200°C, an injection time of 10 seconds, a metal mold temperature and a cooling time under the conditions described in Table 3. It was molded down to obtain a business card-sized plate composed of a part with a thickness of 1 mm and a part with a thickness of 0.5 mm.

The transparency (haze) and crystallinity of the obtained plate were measured. The results are shown in Table 3.

Comparative Examples 10-11

Granulation was carried out in the same manner as in Example 24 except that the amide compound was not added. The pellets obtained were dried, and molded under the conditions shown in Table 3 in the same manner as in Examples to obtain plates with the same dimensions as in Examples. Table 3 shows the measurement results of physical properties of the obtained plates.

Comparative Examples 12-13

Pellets were produced in the same manner as in Example 24 except that no ester-based plasticizer was added. The obtained pellets were dried and molded in the same manner as in Examples, and molded under the conditions shown in Table 3 to obtain plates with the same dimensions as in Examples. Table 3 shows the measurement results of physical properties of the obtained plates.

Comparative Examples 14-15

Pellets were produced in the same manner as in Example 24 except that the amide compound and the ester compound were not added. The pellets obtained were dried, and molded under the conditions shown in Table 3 in the same manner as in Examples to obtain plates with the same dimensions as in Examples. Table 3 shows the measurement results of physical properties of the obtained plates.

In Table 1, Table 2, and Table 3, each symbol of a to h means an amide compound, and each symbol of A to K means an ester plasticizer.

1) Amide compounds

a: trimesic acid tricyclohexylamide (melting point: 384°C)

b: trimesic acid tris(4-methylcyclohexylamide) (melting point: 366°C)

c: trimesic acid tris(tert-butylamide) (melting point: 368°C)

d: 1,4-cyclohexanedicarboxylic acid bis(2-methylcyclohexylamide) (melting point: 363°C)

e: 1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide (melting point: 381°C)

f: 2,6-naphthalene dicarboxylic acid dicyclohexylamide (melting point: 385°C)

g: 1,4-cyclohexanedicarboxylic acid dibenzylamide (melting point: 310°C)

h: 1,2,3,4-butanetetracarboxylic acid tetraanilide (melting point: 331°C)

2) Ester plasticizer

A: Glycerol triacetate

B: Acetyl tributyl citrate

C: Tris(2-ethylhexyl citrate)

D: Triethylene glycol bis(2-ethylhexanoate)

E: Diethylene glycol dibenzoate

F: Di(2-ethylhexanoate) of polyethylene glycol with a number average molecular weight of 300

G: Dibenzoate of polyethylene glycol with a number average molecular weight of 200

H: Tripropylene glycol bis(2-ethylhexanoate)

I: Dipropylene glycol dibenzoate

J: Bis(2-ethylhexanoate) of polypropylene glycol with a number average molecular weight of 400

F: Dibenzoate of polypropylene glycol with a number average molecular weight of 400

Table 1 Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 Amide compounds type a a a a a a b c d e f g h a a a a a Amount added (parts) 0.5 0.5 0.5 0.1 0.3 1.0 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Ester plasticizer type G G G G G G G G G G G G G A B C D. E. Amount added (parts) 25 20 30 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 Physical properties of particles Tc(℃)Tg(℃)Tm(℃) 11825157 11931159 11620154 9926157 11826157 11624156 10826157 10227157 10627157 10226157 9728157 10925156 12725157 11529158 11632159 11731158 11828157 11729157 Crystallization conditions Temperature (℃) Time (min) 602 602 602 602 602 602 602 602 602 602 602 602 602 602 602 602 602 602 Physical properties of molding Haze (%/0.5mm) twenty three 16 27 20 twenty one 25 twenty three 20 twenty two twenty two 28 twenty four 25 15 17 16 19 18 Crystallinity (%) 40.5 34.8 45.9 38.5 39.4 42.1 40.7 36.2 38.5 39.8 40.3 38.6 37.5 32.3 34.5 33.8 36.0 35.6 Tensile test yield strength (MPa) elongation (%) 10.1340 27.6320 18.5430 19.9420 20.3418 21.6395 20.8410 19.4420 20.0416 20.4415 20.6415 19.9410 19.2405 22.1373 22.3375 22.1370 21.9380 21.7382 Heat resistance test ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

Table 2 Example comparative example 19 20 twenty one twenty two twenty three 1 2 3 4 5 6 7 8 9 Amide compounds type a a a a a - - - - - a a - - Amount added (parts) 0.5 0.5 0.5 0.5 0.5 0 0 0 0 0 0.5 0.5 0 0 Ester plasticizer type f h I J K G G B E. I - - - - Amount added (parts) 25 25 25 25 25 25 25 25 25 25 0 0 0 0 Physical properties of particles Tc(℃)Tg(℃)Tm(℃) 11724157 11729157 11830157 11733157 11635158 10127157 10127157 10432159 9830157 10031157 12954168 12954168 10559168 10559168 Crystallization conditions Temperature (℃) Time (min) 602 602 602 602 602 602 1002 602 602 602 602 1002 602 1002 Physical properties of molding Haze (%/0.5mm) twenty four 17 16 15 16 14 87 13 13 12 7 85 6 12 Crystallinity (%) 41.3 35.1 34.0 32.9 33.1 22.0 41.2 18.3 18.5 15.1 6.1 34.6 5.0 9.8 Tensile test yield strength (MPa) elongation (%) 20.5420 23.0365 22.8361 22.7363 22.8360 10.0335 21.4290 12.0292 10.1320 10.4309 60.55 61.84 57.95 58.34 Heat resistance test ○ ○ ○ ○ ○ △ ○ x x x x ○ x x

table 3 Amide compounds Ester plasticizer Physical properties of particles Metal mold temperature (℃) Cooldown (seconds) Mold release Physical properties of molding type Amount added (parts) type Amount added (parts) Tc(°C) Tg(°C) Tm(°C) Haze (%/0.5mm) Crystallinity Heat resistance test Example twenty four a 0.5 G 15 122 34 160 90 40 good 65 45.6 ○ 25 a 0.5 G 15 122 34 160 100 40 good 67 47.3 ○ 26 a 0.5 B 15 120 42 162 90 40 good 66 44.5 ○ comparative example 10 - 0 G 15 101 38 160 90 40 bad - 23.4 x 11 - 0 G 15 101 38 160 100 180 good 91 44.3 ○ 12 a 0.5 - 0 129 54 168 90 40 bad - 24.9 x 13 a 0.5 - 0 129 54 168 100 150 good 86 41.6 ○ 14 - 0 - 0 105 59 168 90 40 bad - 9.1 x 15 - 0 - 0 105 59 168 100 300 good 92 40.3 ○

In Table 3, for Comparative Examples 10, 12, and 14, the molded product hardly crystallized when the cooling time was 40 seconds, so it was soft and poor in mold release. At this time, it deformed, so it could not be accurately measured Molded products with haze. On the other hand, in Comparative Examples 11, 13, and 15, metal release was good, but in order to improve heat resistance, long-term cooling of 150 to 300 seconds was required, and transparency was also poor.

Industrial availability

The present invention is to provide a molded article composed of a lactic acid-based polymer having transparency and crystallinity (heat resistance). The present invention imparts both transparency and crystallinity to a molded article composed of a lactic acid-based polymer.

In addition, according to the method for producing a molded article composed of a lactic acid-based polymer of the present invention, the crystallization rate can be increased in the above-mentioned crystallization step, so that the molding cycle can be shortened.

Furthermore, when a molded article of a lactic acid-based polymer is produced using the lactic acid-based polymer composition of the present invention, the releasability of the molded article obtained from metal molding is good.

Claims (14)

1. A lactic acid-based polymer composition, characterized in that it contains at least (i) at least one amide compound represented by general formula (1), (ii) derived from citric acid derivatives and polyalkylene glycols at least one of the ester plasticizers selected from the composition group, and (iii) Lactic acid polymers, In the formula, ^R represents a saturated or unsaturated aliphatic polycarboxylic acid residue with 2 to 30 carbon atoms, a saturated or unsaturated alicyclic acid polycarboxylic acid residue with 4 to 28 carbon atoms, or a carbon atom Aromatic polycarboxylic acid residues with a number of 6-28, R ² represents an alkyl group with 1 to 18 carbon atoms, an alkenyl group with 2 to 18 carbon atoms, a cycloalkyl group or a cycloalkenyl group with 3 to 12 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a general A group represented by formula (a), general formula (b), general formula (c), or general formula (d); In each of the above formulas, ^R represents an alkyl group with 1 to 18 carbon atoms, an alkenyl group with 2 to 18 carbon atoms, an alkoxy group with 1 to 18 carbon atoms, a cycloalkyl group with 3 to 18 carbon atoms, Phenyl or halogen atom; R ⁴ represents a linear or branched alkylene group with 1 to 4 carbon atoms, R ⁵ and R ⁶ are the same as the definition of R ³ above, and R ⁷ is the same as the definition of R ⁴ above , R ⁸ are as defined above for R ³ , a is an integer of 2-6, b is an integer of 1-5, c is an integer of 0-5, d is an integer of 1-5, and e is an integer of 0-5. 2. The lactic acid polymer composition according to claim 1, wherein ^R represents 1,4-cyclohexanedicarboxylic acid residue, 2,6-naphthalene dicarboxylic acid residue, trimesic acid residue Or 1,2,3,4-butane tetracarboxylic acid residues. 3. The lactic acid-based polymer composition according to claim 1, wherein R ¹ represents a trimesic acid residue. 4. The lactic acid polymer composition according to claim 1, wherein ^R represents 1,4-cyclohexanedicarboxylic acid residue, 2,6-naphthalene dicarboxylic acid residue, trimesic acid residue Or 1,2,3,4-butane tetracarboxylic acid residue, R ² represents tert-butyl, cyclohexyl, phenyl, 2-methylcyclohexyl, 4-methylcyclohexyl or benzyl. 5. The lactic acid polymer composition according to claim 4, wherein the amide-based amine compound is composed of at least one selected from the following compounds, i.e. trimesic acid tricyclohexylamide, trimesic acid Tris(2-methylcyclohexylamide), trimesic acid tris(4-methylcyclohexylamide), 1,4-cyclohexanedicarboxylic acid dicyclohexylamide, 1,4-cyclohexanedicarboxylate Acid bis(2-methylcyclohexylamide), 1,4-cyclohexanedicarboxylic acid dibenzylamide, 2,6-naphthalene dicarboxylic acid dicyclohexylamide, 1,2,3,4-butane tetracarboxylic acid tetracyclohexylamide and 1,2,3,4-butanetetracarboxylic acid tetraanilide. 6. The lactic acid-based polymer composition according to claim 1, wherein the ester-based plasticizer is at least one of citric acid derivatives. 7. The lactic acid-based polymer composition according to claim 1, wherein the ester-based plasticizer is at least one of polyalkylene glycol derivatives. 8. The lactic acid polymer composition according to claim 1, wherein the citric acid derivative is formed from acetyl citrate tri-C _1-18 alkyl ester and citrate tri-C _1-18 alkyl ester At least one selected from . 9. The lactic acid polymer composition according to claim 1, wherein the polyalkylene glycol derivative is at least one selected from the following compounds, i.e. diethylene glycol di-C _2-18 aliphatic Carboxylate, triethylene glycol di-C _2-18 aliphatic carboxylate, tetraethylene glycol di- _{C 2-18} aliphatic carboxylate, polyethylene glycol di-C _2-18 aliphatic carboxylate, Diethylene glycol diaromatic carboxylate, triethylene glycol diaromatic carboxylate, tetraethylene glycol diaromatic carboxylate, polyethylene glycol diaromatic carboxylate, dipropylene glycol di-C _2-18 fatty acid Aliphatic carboxylic acid ester, tripropylene glycol di-C _2-18 aliphatic carboxylic acid ester, tetrapropylene glycol di-C _2-18 aliphatic carboxylic acid ester, polypropylene glycol di-C _2-18 aliphatic carboxylic acid ester, dipropylene glycol di Aromatic carboxylate, tripropylene glycol diaromatic carboxylate, tetrapropylene glycol diaromatic carboxylate, and polypropylene glycol diaromatic carboxylate. 10. The lactic acid-based polymer composition according to claim 1, wherein the above-mentioned lactic acid-based polymer has a weight average molecular weight of 50,000 or more. 11. The lactic acid-based polymer composition according to claim 1, which contains 0.01 to 10 parts by weight of an amide compound and 1 to 300 parts by weight of an ester-based plasticizer based on 100 parts by weight of a lactic acid-based polymer. 12. A molded article obtained by molding the lactic acid-based polymer composition according to any one of claims 1 to 11. 13. A transparent molded article comprising the lactic acid-based polymer composition according to any one of claims 1 to 11, having a crystallinity of 30% or more and a haze of 70% at a thickness of 0.5 mm. %the following. 14. A manufacturing method, which is a manufacturing method of the lactic acid-based polymer molded body according to claim 13, comprising the following steps: 1) filling the melt of the lactic acid polymer composition in granular form into a metal mold to crystallize it in the metal mold, or 2) Extrude the melt of the lactic acid-based polymer composition in granular form from a T-die extrusion molding machine, crystallize it with a chilled roll, The crystallization is carried out at a temperature between Tc and Tg, wherein Tc is the temperature at which crystallization of the lactic acid-based polymer composition begins, obtained by measuring the composition of the lactic acid-based polymer by differential scanning calorimetry, and Tg is Glass transition temperature of lactic acid-based polymer composition.